Utilization of photocatalytic, photochemicallytic and dissociation reactions in combinations with radiation and oxidizing agents

ABSTRACT

Methods, systems, and apparatuses for producing one or more of trioxygen, reactive nitrogen species, hydrogen, oxygen, and electronically modified oxygen derivatives from oxidizing agents that are exposed to certain frequencies of radiation, exposed for certain amounts of time, and exposed to certain intensities of radiation. The oxidizing agent or oxidizing agents can be exposed to multiple frequencies of radiation and multiple exposures of radiation. A combination of one or more oxidizing agents and radiation of certain wavelengths forms a synergistic reaction. The synergistic reaction generates, among other agents, RNS, EMODs, which can further produce variation in the standard chemical reaction associated with the decomposition of the oxidizing agent. This reaction variation may produce RNS, trioxygen, hydrogen and/or its isotopes, and/or oxygen and/or its isotopes and/or electronically modifies oxygen derivatives. This synergistic reaction has a relationship to EMOD creation, Oxygen and its isotope generation and hydrogen and its isotope generation.

BACKGROUND

Oxidizing agents such as hydrogen peroxide have received increasingattention as an energy carrier. To achieve sustainable energy,photocatalytic splitting of oxidizing agents such as hydrogen peroxideis a desirable reaction for on-site hydrogen generation. Numerousapplications across many industries have been found. From energy storageand production, medical, food, environmental and others, this previouslyunknown method of combining, photocatalytic, photochemicallytic anddissociation reactions with radiation and oxidizing agents opens a newfrontier. This reaction has not previously been reported becauseconventional photocatalysis decomposes oxidizing agents bydisproportionation and by promoting oxidizing agent reduction instead ofhydrogen liberation. Here we report the successful example of oxidizingagent splitting. Trioxygen associates with the reactants and suppressesthe reactant reduction, thus promoting hydrogen liberation. The organicphotocatalytic system may provide a basis of photocatalytic andphotochemicallytic oxidizing agent splitting. An oxidizing agent is achemical species that undergoes a chemical reaction in which it gainsone or more electrons. Also, an oxidizing agent can be regarded as achemical species that transfers electronegative atoms, usually oxygen,to a substrate. The oxidizing agent can be called an oxygenation reagentor oxygen-atom transfer (OAT) agent. Oxidation reactions may involveoxygen atom transfer reactions and hydrogen atom abstraction which is areaction where removal of an atom or group from a molecule by a radicaloccurs. The UV radiation commonly used in antimicrobial processes isknown as UV-C. Ultra-Violet (UV) light is invisible to the human eye andis divided into UV-A, UV-B and UV-C. UV-C is found within 100-280 nmrange. The germicidal action of UV-C is maximized at approximately 265nm with reductions on either side. UV-C sources typically have theirmain emission at 254 nm.

As a result, germicidal lamps can be effective in breaking down the DNAof microorganisms. This means that they cannot replicate and causedisease. UV radiation also can be used to produce or eliminate trioxygenwhich can be a hazardous Reactive Oxygen Species. Reactive nitrogenspecies (RNS) is a subset of free oxygen radicals called reactive oxygenspecies (ROS). Trioxygen can also be used as a catalyst to convert H2Oto products that exhibit health benefits, antimicrobial properties andhave wide commercial uses.

In chemistry, photocatalysis is the acceleration of a photoreaction inthe presence of a catalyst. Photocatalysts are materials that change therate of a chemical reaction on exposure to light. In catalyzedphotolysis, light is absorbed by a substrate. Photocatalytic activity(PCA) depends on the ability of the catalyst to create electron-holepairs, which utilize electronically modified oxygen derivatives whichare then able to undergo secondary reactions. Typically, two types ofphotocatalysis reactions are recognized, homogeneous photocatalysis andheterogeneous photocatalysis. Homogeneous photocatalysis: when both thephotocatalyst and reactant are in the same phase, i.e. gas, solid, orliquid, such photocatalytic reactions are termed as homogeneousphotocatalysis. Heterogeneous photocatalysis: when both thephotocatalyst and reactant are in different phases, such photocatalyticreactions are classified as heterogeneous photocatalysis. When aphotocatalyst is exposed to radiation of the desired wavelength(sufficient energy), the energy of photons is absorbed by an electron(e−) of valence band and it is excited to conduction band. In thisprocess a hole (h+) is created in valence band. This process leads tothe formation of photo-excitation state, and e− and h+ pair isgenerated. The hydroxyl radical is generated in both types of reaction.The difference in the two types of photocatalytic reactions are theplacements of the reactants and the photocatalysts

SUMMARY

In one embodiment, a method for generating photo oxidation products,photocatalytic products and/or photochemicallytic products which includeone or more of reactive nitrogen species, hydrogen and its isotopes,oxygen and its isotopes, and electronically modifies oxygen derivatives,reactive oxygen species, trioxygen, and free radicals, may be providedand may include applying at least one oxidizing agent to a target; andbefore, and/or during, and/or after the at least one oxidizing agent isapplied to the target, applying radiation to the oxidizing agent, whichforms a synergistic reaction and produces the photo oxidation products,where the photo oxidation products comprise at least trioxygen andhydroxyl radical, and wavelengths that photodissociate, eliminate, orreduce trioxygen are excluded from the radiation.

In another embodiment, a system for performing the steps of the abovemethod may be provided. The system can include a reaction area, in whichthe at least one oxidizing agent functions together with the radiationof certain wavelengths to lead to a synergistic reaction, so that theproducts of the reaction can be collected and separated any time duringthe reaction if desired, at least one oxidizing agent introducingcomponent for applying the at least one oxidizing agent to the target,and at least one radiation emitting component for creating the radiationwherein wavelengths that can photodissociate, eliminate, or reducetrioxygen are excluded from the radiation.

BRIEF DESCRIPTION OF THE DRAWINGS

Advantages of exemplary embodiments of the system, retainer and methodof providing therapeutic treatment will be apparent from the followingdetailed description of the exemplary embodiments. The followingdetailed description should be considered in conjunction with theaccompanying figures in which:

FIG. 1 is an exemplary diagram showing a reaction can occur from areactant molecule via an intermediate such as hydroperoxyl to form antrioxygen molecule.

FIG. 2 is an exemplary diagram showing a “stored” oxidizing effect thatcan be tapped to provide reactive oxygen species as needed, and the“stored” oxidizing effect feeds the looped chain reaction so thatreactive oxygen species are generated until one of the reactants isdepleted.

DETAILED DESCRIPTION

Aspects of the invention are disclosed in the following description andrelated drawings directed to specific embodiments of the invention.Alternate embodiments may be devised without departing from the spiritor the scope of the invention. Additionally, well-known elements ofexemplary embodiments of the invention will not be described in detailor will be omitted so as not to obscure the relevant details of theinvention. Further, to facilitate an understanding of the descriptiondiscussion of several terms used herein follows.

As used herein, the word “exemplary” means “serving as an example,instance or illustration.” The embodiments described herein are notlimiting, but rather are exemplary only. It should be understood thatthe described embodiments are not necessarily to be construed aspreferred or advantageous over other embodiments. Moreover, the terms“embodiments of the invention”, “embodiments” or “invention” do notrequire that all embodiments of the invention include the discussedfeature, advantage or mode of operation.

In the system displayed herein, a unique method of utilizing bothhomogeneous and heterogeneous reactions is described. By utilizing bothtypes of PCA, a self-sustaining reaction is produced resulting inelectronically modified oxygen derivatives that are continuouslyproduced as long as reactants are present. Trioxygen is one of thepotential photocatalysts. This results in an increased efficacy and ashelf life of increased and sustainable reactivity previously notproducible with oxidizing agents.

The embodiments relate to producing one or more of reactive nitrogenspecies, trioxygen, hydrogen and/or its isotopes, and/or oxygen and/orits isotopes and/or electronically modifies oxygen derivatives, reactiveoxygen species, free radicals, oxidizing molecules, oxygen-atom transfer(OAT) agents, oxidizing agents and/or various related species fromoxidizing agents that are exposed to certain frequencies of radiation,exposed for certain amounts of time and exposed to certain intensitiesof radiation. The oxidizing agents can be exposed to multiplefrequencies of radiation and multiple exposures of radiation. Theradiation can be supplied to the oxidizing agents continuously or inbursts or pulses. During research into the effects of radiation onoxidizing agents, a discovery was made that offers a revolutionary andmulti-disciplinary advancement to science. The methods displayed providea new paradigm to perform photocatalytic oxidation of substrates usingradiation as energy input, trioxygen as the catalyst and oxidizingagents as the oxygen source and dissociation reactions to minimizehindrances to the reactions. Understanding the chemistry of this newparadigm is essential for utilizing the reactivity. Photocatalyticactivity (PCA) is commonly applied to a target in two distinct ways.

Further, the embodiments utilize both methods of applying photocatalyticactivity to generate a unique reaction that continues even after theradiation that initiates the PCA is discontinued. The present research,which is reflected in the embodiments, explored PCA utilizing radiationand a significant discovery was made. It has now been found that thedestruction of trioxygen (O3) by certain wavelengths of radiationprevents or retards reactions involved in the photocatalytic effects.The catalyst, trioxygen, was being eliminated by certain wavelengths ofradiation that encourage dissociation. By altering the production oravailability of trioxygen, the reaction may include steps that allowsand encourages or alternatively prevents or retards the generation ofproducts such as oxygen and hydrogen, reactive nitrogen species,electronically modified oxygen derivatives and others.

In one exemplary embodiment, it may be understood that after trioxygenis produced it will decay rapidly, because trioxygen is an unstablecompound with a relatively short half-life. The half-life of trioxygenin liquid is a lot shorter than in air. Trioxygen decays in liquidspartly in reactions with hydroxyl radicals. The assessment of atrioxygen decay process always involves the reactions of two species:trioxygen and hydroxyl radicals. When these hydroxyl radicals are thedominant particles in the solution, it is called an advanced oxidationprocess (AOP). The decay of trioxygen in contact with hydroxyl radicalsin liquids is characterized by a fast initial decrease of trioxygen,followed by a second phase in which trioxygen decreases by first orderkinetics. Dependent on the quality of the liquids, the half-life oftrioxygen is in the range of seconds to hours in common testing. Factorsinfluencing the decomposition of trioxygen in liquids are temperature,pH, ions, cations, environment and concentrations of dissolved matterand UV light.

As mentioned above, trioxygen decomposes partly in hydroxyl radicals.When the pH value increases, the formation of hydroxyl radicalsincreases. In a solution with a high pH value, there are more hydroxideions present, see formulas 0-1 and 0-2 below. These hydroxide ions actas an initiator for the decay of trioxygen:

O₃+OH⁻→HO₂ ⁻+O₂  Equation 0-1

O₃+HO₂—→^(•)OH+O₂ ^(•−)+O₂  Equation 0-2

The radicals that are produced during reaction 0-2 can introduce otherreactions with trioxygen, causing more hydroxyl radicals to be formed.Dependent on the nature of dissolved matter in a liquid, these canaccelerate or slow down the decay of trioxygen. Substances thataccelerate this reaction are called promoters. Inhibitors are substancesthat slow down the reaction. When a liquid is infused with trioxygen,one often uses the term ‘scavenging capacity’ in reference to the decayrate of the trioxygen. Scavengers and inhibitors are entities that reactwith hydroxyl radicals and slow down the reaction between trioxygen andhydroxyl radicals. Some common methods of inhibiting the decay oftrioxygen involve lowering the pH of the target liquid and usingdeionized solutions as dilutants when possible.

In further exemplary embodiments, oxidative reactions due tophotocatalytic homogenous effect may be described and utilized asfollows:

The mechanism of hydroxyl radical production can follow paths such as:

O₃ +hv→O₂+O  Equation 1

O+H₂O→•OH+•OH  Equation 2

O+H₂O→H₂O₂  Equation 3

H₂O₂ +hv→•OH+•OH  Equation 4

Similarly, the Fenton system produces hydroxyl radicals by the followingmechanism:

Fe²⁺+H₂O₂→HO•+Fe³⁺+OH⁻  Equation 5

Fe³⁺+H₂O₂→Fe²⁺+HO•2+H⁺  Equation 6

Fe²⁺+HO•→Fe³⁺+OH⁻  Equation 7

In photo-Fenton type processes, additional sources of OH radicals shouldbe considered: through photolysis of H₂O₂, and through reduction of Fe³⁺ions under radiation:

H₂O₂+radiation→HO•+HO•  Equation 8

Fe³⁺+H₂O+radiation→Fe²⁺+HO•+H⁺  Equation 9

Oxidative reactions due to photocatalytic heterogenous effect:

h ⁺+H₂O→H++•OH  Equation 10

2h ⁺+2H₂O→2H⁺+H₂O₂  Equation 11

H₂O₂→2•OH  Equation 12

The reaction of H2O2=H2O+O is typically referenced in most literature asthe predominant disassociation reaction associated with hydrogenperoxide and results in the production of oxygen and water. There are anumber of reaction pathways such as dissociation to hydronium ion andhydroperoxide, and disproportionation to dioxygen and water. Note thatTRIOXYGEN is not produced in the above reactions. Trioxygen isphotodissociated by certain wavelengths of radiation. While trioxygenmay be created, it may also be dissociated depending on the desiredoutcome of the reaction. The table below is a partial list of theproducts of trioxygen dissociation and a partial list of the wavelengthsassociated with those products.

TABLE 1 O(³P) + O₂(³Σ) 1118.4 nm O(³P) + O₂(¹Δ) 599.2 nm O(³P) + O₂(¹Σ)452.6 nm O(¹D) + O₂(³Σ) 402.8 nm O(¹D) + O₂(¹Δ) 307.0 nm O(¹D) + O₂(¹Σ)263.3 nm O(³P) + O(³P) + O(³P) 197.1 nm

In one path, the embodiments describe one or more reactions whereby thetrioxygen is not photodissociated by radiation. Trioxygen then becomes aphotocatalyst for newly discovered reactions. The resulting reaction isone that has not previously been described. Trioxygen is produced andretained when the above-mentioned wavelengths of photodissociation areexcluded. This exclusion coupled with photocatalytic reactionsgenerating one or more of reactive nitrogen species, trioxygen, hydrogenand/or its isotopes, and/or oxygen and/or its isotopes and/orelectronically modifies oxygen derivatives, reactive oxygen species,free radicals, oxidizing molecules, oxidizing agents and/or variousrelated species from oxidizing agents that are exposed to certainfrequencies of radiation. The reaction with OH— is the initialdecomposition step of trioxygen decay, the stability of a trioxygensolution is thus highly dependent on pH and decreases as alkalinityrises. At pH above 8 the initiation rate has, in the presence of radicalscavengers, been shown to be proportional to the concentrations oftrioxygen and OH—. However, in acidic solutions the reaction with OH— isnot the initiation step. Predicted reaction rates below pH 4 including amechanism based only on reaction with OH— are much lower than thosedetermined experimentally. The trioxygen equilibrium reaction belowbecomes significant and the initiation reaction is catalyzed.

The atomic O continues to react with H2O, or forms an excited trioxygenradical, from recombination, that subsequently reacts with H2O, as shownin the two equations below, respectively.

The species formed can then react further, forming other radicals suchas O2-/HO2. The propagating products, HO• and HO2, diffuse and reactwith trioxygen in the continuing the chain reaction. Only lowconcentrations of the terminating species are present in the solutionwhich is why the significant part of the termination reactions belowalso takes place.

An example of an oxidizing agent involved in this reaction;H2O2+radiation between 100 nm and 1200 nm (where the wavelengths causingphotodissociation of trioxygen have been excluded), when H2O2 and thisselective radiation are combined, this reaction yields H2+2HO2 which inturn yields H2O+trioxygen. This looped chain reaction will continue aslong as the correct radiation is present and H2O2 (oxidizing agent) ispresent. The 2 paths of this reaction can yield various products butparticularly H2 and O2 or yield 2HO2. The trioxygen that is created onthis path enters and exists in a looped chain reaction with H2O and thelooped chain reaction will continue to function and is dependent on thesupply of trioxygen or hydroperoxyls generated from reactions oftrioxygen or hydroxyl radicals or generated from reactions of trioxygenwith other reactants. A looped chain reaction includes numerousreactions and potential reactions that may vary depending on variablessuch as temperature, pH, catalysts, and others. The more basic andrecognizable reaction is the looped chain reaction where it is trioxygenthat reacts with water producing at various stages O2, hydroxyls, H2,HO3, HO4, and hydroperoxyls. Exposure of oxidizing agents such ashydrogen peroxide with the entire UV spectrum of radiation produceshydroxyl radicals but limited or no trioxygen due to the wavelengthsthat are present that also destroy trioxygen, which was previouslyundiscovered and, without this step, the products of this reaction couldnot be produced in a sustained looped chain reaction. Furthermore, ifthis step is performed, but performed in the wrong sequence, thereaction will not have the desired results and the sustained loopedchain reaction will not occur. Hydroxyl radicals are very reactive freeradicals, but they only exist for extremely brief periods of timemeasured in nana seconds. This nano second long existence leads to ashort-term effect whereby the hydroxyl radicals exert an influence thatcannot be stored or held in reserve. While this immediate effect hasmany uses, the production of trioxygen by the irradiation of oxidizingagents with radiation of certain wavelengths that exclude thosewavelengths associated with the dissociation of trioxygen producesreactants such as hydroperoxyls that react to form trioxygen. Withtrioxygen in a looped chain reaction, a steady stream of products iscreated, one being a chain of hydroxyl radicals that can now exert amore long-lasting effect. This sustained, looped chain reaction alsoallows for a “shelf life” where the reaction can be maintained andstored for future use even after the radiation exposure has beenterminated. An effect that can now be measured in minutes, hours or daysdue to the continued effect of the reaction products created.

In reference to the discussed reactions, the embodiments explain newdiscoveries whereby the radiation directed at the oxidizing agent altersthe typical reaction. This can be accomplished by excluding wavelengthsof radiation that inhibit the formation of trioxygen or wavelengths thatdestroy trioxygen. This creates and allows trioxygen to function as aphotocatalyst.

The following embodiment relates to the working model of the equationfor the looped chain reaction. In chemical kinetics, an equationdictates that a chemical reaction utilizing oxidizing agents proceedsvia a decomposition reaction where an electron induced decomposition byradiation (excluding wavelengths inhibiting trioxygen formation ordestroying trioxygen) of the oxidizing agent proceeds. X definespotential decomposition by-products such as reactive nitrogen species,hydroxyls, hydroperoxyls, electronically modified oxygen species,hydrogen and oxygen and others. A reaction can occur from a reactantmolecule via an intermediate such as hydroperoxyl to form an trioxygenmolecule, as shown in FIG. 1.

OXIDIZING AGENT+radiation dose (excluding wavelengths that dissociatetrioxygen (O3))→O3+X.

In reference to the above reactions, this embodiment explainsdiscoveries whereby the radiation directed at the oxidizing agent altersthe typical reaction. This can be accomplished by excluding wavelengthsof radiation that inhibit the formation of trioxygen or wavelengths thatdestroy trioxygen. Photochemical reactions are a chemical reactioninitiated by the absorption of energy in the form of light. Theconsequence of molecules' absorbing light is the creation of transientexcited states whose chemical and physical properties differ greatlyfrom the original molecules. Photochemicallytic trioxygen generation(PTG) splits water molecules into H2, O2, and O3. PTG can achieve highdissolution in water without other competing gases found in the coronadischarge method of trioxygen production, such as nitrogen gases presentin ambient air. This method of generation can achieve consistenttrioxygen concentration and is independent of air quality because wateris used as the source material. Production of trioxygen photochemicallywas previously not utilized because of the required wavelength exclusionrequired to produce trioxygen as compared to producing oxygen as thetypical reaction product. However, as described herein, it is possibleto change the production of oxygen by careful selection of radiationwavelengths such that trioxygen is preferentially produced. Previousresearch involving UV radiation utilized bulbs that produced abell-shaped curve of radiation that produced wavelengths of dissociationof compounds and wavelengths creating the same compounds. While theremay have been a greater influence of either the creation or dissociationwavelength, the resulting reaction was at best inefficient.

Thus, in the present embodiments, to generate more trioxygen,wavelengths of radiation that dissociate trioxygen are excluded and thedose of radiation can be increased by increasing the intensity, the timethe radiation is applied and other variables to the dose where some orall variables may be changed. This data helps to demonstrate the natureof the initial complex which decomposes an oxidizing agent uponradiation exposure. Further, multiple reaction sequences are possible.First, comparing the electronic structure of the water and the oxidizingagent molecules, the trioxygen should cleave at least oneoxygen-hydrogen bond of the water molecule in the looped chain reaction,which, in turn, forms the hydroxyl radical plus atomic hydrogen. Thisprocess is endoergic. Two of the hydroxyl radicals can recombine in anexoergic reaction to form an oxidizing agent molecule. The reactionreversibility dictates that upon application of trioxygen to the watermolecule, the latter can decompose in one step to form oxygen atoms plusmolecular hydrogen. The oxygen atom in the presence of trioxygen canreact now with a water molecule by an insertion into an oxygen-hydrogenbond to form hydrogen peroxide but with the continued application oftrioxygen, the generation of H2O2 may be delayed or excluded. As thereaction is delayed, oxygen and hydrogen may be liberated in sufficientquantities to alter the quantity of available components thus preventingor minimizing the production of H2O2. Alternatively, the oxygen atom canadd itself to the oxygen atom of the water molecule forming ashort-lived intermediate which rearranges then via hydrogen migration tothe hydrogen peroxide molecule. These equations display an electroninduced decomposition of two water molecules in close proximity.[(H₂O(X¹A₁))₂] to form a hydrogen peroxide molecule while liberatinghydrogen and oxygen.

H₂O(X¹A₁)+TRIOXYGEN→H(²S_(1/2))+OH(X²Π_(Ω))  Equation 13

2OH(X²Π_(Ω))+TRIOXYGEN→H₂O₂(X¹A)  Equation 14

H₂O₂(X¹A₁)+TRIOXYGEN→O(¹D)+H₂(X¹Σ_(g) ⁻)  Equation 15

O(¹D)+H₂O(X¹A₁)+TRIOXYGEN→H₂O₂(X¹A)  Equation 16

O(¹D)+H₂O(X¹A₁)+TRIOXYGEN→[OOH₂(X¹A)]+TRIOXYGEN→H₂O₂(X¹A)   Equation 17

(A)[(H₂O(X¹A₁))₂]+TRIOXYGEN→[H(²S_(1/2)) . . . HO(X²Π_(Ω)) . . .OH(X²Π_(Ω)) . . .H(²S_(1/2))]+TRIOXYGEN→H₂O₂(X¹A)+2H(²S_(1/2))  Equation 18

(B)[(H₂O(X¹A₁))₂]+TRIOXYGEN→[H₂(X¹Σ_(g) ⁺) . . . H₂O(X¹A₁) . . .O(¹D)]+TRIOXYGEN→H₂(X¹Σ_(g) ⁺)+H₂O₂(X¹A)  Equation 19

(C)[(H₂O(X¹A₁))₂]+TRIOXYGEN→[H₂(X¹Σ_(g) ⁺) . . . H₂O(X¹A₁) . . .O(¹D)]+TRIOXYGEN→[H₂(X¹Σ_(g) ⁺) . . . H₂OO(X¹A)]+TRIOXYGEN . . . HO3 . .. HO4→H₂(X¹Σ_(g) ⁺)+H₂O₂(X¹A)   Equation 20

As can be seen above from the equations, the water solution still storeshighly reactive radicals such as RNS, EMODs, hydroxyl radicals,hydroperoxyls, and the like. Hydroxyl radicals can diffuse and once theyencounter a second hydroxyl radical, they can recombine to form hydrogenperoxide. As described herein, it may be understood that upon adecomposition of the water molecules, the oxygen atoms are formed in thefirst excited state. When the radiation exposure stops and the trioxygenis depleted, the production of excited atoms ceases, too. Thisreinforces the fact that, without removing the wavelengths thatdissociate trioxygen, this reaction cannot proceed as described. Thereactivity of ground state atoms with water is different compared to thedynamics of the trioxygen excited counterparts generated during exposureto trioxygen described in this patent via stated equations. The data andrelated discussion on the formation of the hydrogen peroxide moleculealso help to explain the synthesis of atomic and molecular hydrogenduring the trioxygen exposure of the oxidizing agent and/or water orsolution or combination of solution composition. Here, the equationsindicate that molecular hydrogen can be formed in a one-step mechanismvia trioxygen decomposition of the water molecule driven by thetrioxygen dose applied to the solution. Alternatively, the hydrogenatoms formed can recombine to form molecular hydrogen. The detection ofhydrogen atoms during the trioxygen exposure of the oxidizing agent orwater or solution or combination of solution composition phase is adirect proof that the reactions take place. Likewise, the observation ofoxygen atoms during the trioxygen exposure suggests that the reactionsare also an important pathway of oxygen production. The matrix may storehydrogen as hydronium or other isotopes of hydrogen and as suspended“bubbles” of hydrogen even when the radiation exposure is terminated andtrioxygen has ceased to be produced. By placing the matrix in a sealedcontainer so that the suspended gases are not allowed to escape,pressure that builds up maintains the reactivity and this potential canbe stored for future use.

Hydroxyl radicals (OH) are formed via a decomposition of a watermolecule upon exposure to trioxygen. This trioxygen driven, looped chainreaction, generates hydrogen, oxygen, free radicals as well as oxidizingmolecules including however, but not limited to, electronically modifiedoxygen derivatives from water or solutions containing oxidizing agentsthat are exposed to radiation which when introduced to an effectiveamount of a composition comprising water and/or an oxidizing agentcompound or other compounds or solutions then exposing the compositionto trioxygen, where the composition including the water and/or oxidizingagent compound, solution or both, functions together with trioxygen tolead to a reaction producing hydrogen and/or its isotopes, and/or oxygenand/or its isotopes and/or electronically modifies oxygen derivativesand or solutions derived or indirectly derived resulting from theexposure of the wavelength(s) in the looped chain reactions and theresultant trioxygen used in the looped chain reactions or the synergytherein. Also, it can be shown that there is a decomposition of the HO₂radical to molecular oxygen plus atomic hydrogen. Finally, to generatethe HO₂ radical, another reaction is hydrogen atoms reacting withmolecular oxygen but with the application of the correct wavelengths ofradiation to the oxidizing agent undergoing this reaction in the loopedchain reactions, the excited state of produced hydrogen atoms and theproduced molecular oxygen and the generation of trioxygen can beretarded or stopped by the discontinuance of the radiation used. Theexcited state can be preserved by sealing the reactants so that producedgases are maintained, and this allows for the reactive potential to bestored.

Thus, these embodiments uncover a significant reaction sequence that hasnot been previously known or understood. By exposing an oxidizing agentto certain doses of radiation, hydrogen is liberated from the reaction.Hydroperoxyls are produced and trioxygen is produced when wavelengthsthat dissociate trioxygen are eliminated or reduced in intensity. Thisreaction generates hydrogen, oxygen, trioxygen and other free radicalsas well as oxidizing molecules including however not limited toelectronically modified oxygen derivatives from oxidizing agents orsolutions containing oxidizing agents that are exposed to certainwavelengths of radiation which when introducing an effective amount of acomposition comprising an oxidizing agent compound or other compounds orsolutions then exposing the composition to radiation of certainwavelengths while excluding the wavelengths that would disallow theformation of trioxygen, wherein the composition comprising the oxidizingagent compound, solution or both, functions together with the radiationof certain wavelength or wavelengths to lead to a reaction producingtrioxygen, hydrogen and/or its isotopes, and/or oxygen and/or itsisotopes and/or electronically modifies oxygen derivatives and orsolutions derived or indirectly derived resulting from the exposure ofsaid wavelength(s) or the synergy therein. The oxidizing potential oftrioxygen is slightly less than the oxidizing potential of hydroxylradicals, but it is greater than the oxidizing potential of hydrogenperoxide. While the commonly accepted lifetime of hydroxyl radicals is afew nanoseconds, trioxygen has been shown to maintain its reactivity forhours. The ability of trioxygen to linger for an extended period allowsfor a “stored” oxidizing effect. The “stored” oxidizing effect can betapped to provide reactive oxygen species as needed and the “stored”oxidizing effect feeds the looped chain reaction so that reactive oxygenspecies are generated until one of the reactants is depleted. FIG. 2reflects testing that displays this “stored” effect. When comparing thecontrol versus the enhanced solution, there is over a 5-log increase inefficacy with the enhanced solution. By employing the looped chainreactions, we have increased the efficacy and reserved the use of theelectronically modified oxygen derivatives that are being continuouslygenerated so that they are available for use over an extended period oftime.

The equations are exemplary and are non-limiting with respect towavelengths, time of irradiation, intensity of radiation or total doseof radiation. By exposing the oxidizing agent or agents to radiation ofbetween 100 nm-1200 nm, a synergistic reaction occurs creating trioxygenand other electronically modified oxygen derivatives and disrupting thetypical disassociation reaction of the oxidizing agent or agents.Chemicals such as oxidizing agents exist in a state of flux whereby,they disassociate and reassociate as self-ionization reactions occur.When alterations of the expected disassociation reactions occur, newcompounds or variations in compound concentrations occur. These newcompounds or variations in compounds created in the synergistic reactionenable a known oxidizing agent to create reactions that have not beenobserved or reported previously. By restricting the radiation applied tothe oxidizing agent so that dissociation of trioxygen is reduced oreliminated, a reaction is produced that has previously not beenobserved. This is shown by the radiation typically produced as havingwavelengths that dissociate trioxygen when said radiation is applied tooxidizing agents. Restricting the dissociation of trioxygen has producedreaction products that have not been described for this reactionpreviously or that have not been produced in quantities that are shownin this patent application.

The reactants may contain enzymes, stabilizers or other substances thataffect the overall reaction rate. Enzymes, stabilizers and/or othersubstances can be destroyed or inactivated by temperature variations, pHshifts and other means. These may be employed to arrive at the mostfavorable reaction outcomes. It is understood that phosphoric acid(H₃PO₄) is generally added to commercially available oxidizing agentsolutions such as hydrogen peroxide as a stabilizer to inhibit thedecomposition of the oxidizing agent. Several types of reagents, such asH₃PO₃, uric acid, Na₂CO₃, KHCO₃, barbituric acid, hippuric acid, urea,and acetanilide, have also been reported to serve as stabilizers foroxidizing agents such as hydrogen peroxide. These stabilizers have beenshown to have a catalyst effect on the reaction, but the reaction mayproceed with or without stabilizers present in oxidizing agents, asdesired.

The embodiments describe new methods and techniques that have not beendescribed or understood previously. By altering the typicaldisassociation wavelength of radiation applied to oxidizing agents, theensuing reaction generates previously unrecorded reaction byproductsand/or quantities of byproducts.

The embodiments demonstrate the new discovery of altering the expectedreactions found by the disassociation of trioxygen while radiation ofcertain wavelengths is targeted to oxidizing agents and by so alteringthe expected disassociation compounds are generated that have not beenreported from the typical disassociation reactions. This discovery hasapplications in many industries. By increasing the efficacy of oxidizingagents, common chemical reactions involving oxidizing agents may beaccomplished using less volume and/or a lower concentration of oxidizingagents. Oxidizing agents can be used to precipitate material out ofsolution. Increasing the efficacy of the oxidizing agent allows for thisprecipitation with less oxidizing agent. Oxidizing agents haveantimicrobial properties. By increasing the antimicrobial efficacy withthe methods described herein, concentrations of oxidizing agentsutilized can be reduced while efficacy can be maintained or increased.By increasing the availability of ROS in the irradiated oxidizing agentsolution, current applications of oxidizing agents in the semiconductorindustry, paper industry, petrochemical industry and other commercialapplications can be accomplished faster and/or more economically and/ormore environmentally responsibly. The uses of the methods describedherein are too numerous to list but are widespread in diverse industriesfrom oil and gas to health care and beyond.

The foregoing description and accompanying figures illustrate theprinciples, preferred embodiments and modes of operation of theinvention. However, the invention should not be construed as beinglimited to the particular embodiments discussed above. Additionalvariations of the embodiments discussed above will be appreciated bythose skilled in the art.

Therefore, the above-described embodiments should be regarded asillustrative rather than restrictive. Accordingly, it should beappreciated that variations to those embodiments can be made by thoseskilled in the art without departing from the scope of the invention asdefined by the following claims.

1. A method for generating one or more of hydrogen, isotopes ofhydrogen, oxygen, and isotopes of oxygen and for electronicallymodifying oxygen derivatives, reactive oxygen species (ROS), trioxygen,and free radicals, comprising: applying to a target liquid having avolume and a pH, at least one oxidizing agent in an amount from lessthan 1 part per million to 50 percent or more of the volume of thetarget liquid to produce in the target liquid one or more of hydrogenand its isotopes, and oxygen and its isotopes when exposed to radiationhaving a wavelength in a range of 300 nanometers through 600 nanometers;applying radiation having a wavelength in a range of 300 nanometersthrough 600 nanometers to the at least one oxidizing agent at leastbefore, during, and/or after the at least one oxidizing agent is appliedto the target liquid to form a reaction and produce in the target liquidthe one or more of hydrogen and its isotopes, and oxygen and itsisotopes, which comprise at least trioxygen and hydroxyl radical; andadjusting the pH of the target liquid to stabilize the trioxygen orreact the trioxygen with hydroxyl radical, and optionally applyingenzymes or applying stabilizers to affect the overall reaction rate, thestabilizers being selected from the group consisting of H₃PO₃, uricacid, Na₂CO₃, KHCO₃, barbituric acid, hippuric acid, urea, acetic acidand acetanilide, wherein wavelengths of 307 nm, 402 nm, 452 nm, and 599nm, which photodissociate, eliminate, or reduce trioxygen, are excludedfrom the radiation, wherein substances that aid in affecting the overallreaction rate are the trioxygen produced by the reaction and theoptionally applied enzymes or stabilizers, and wherein the reaction isable to proceed with or without said enzymes, said stabilizers or othersubstances that affect the overall reaction rate. 2.-3. (canceled) 4.The method of claim 1, wherein the radiation source is a bulb or LED,and the radiation is applied directly or indirectly to at least one ofthe oxidizing agent, the trioxygen or the target liquid.
 5. The methodof claim 1, wherein an oxidizing agent dispenser is used to apply the atleast one oxidizing agent to the target liquid, and the oxidizing agentdispenser is a pump, a mister, a diffuser, or an electrostatic sprayer.6.-7. (canceled)
 8. The method of claim 1, wherein the irradiated atleast one oxidizing agent is used to precipitate material out ofsolution.
 9. The method of claim 1, wherein the irradiated at least oneoxidizing agent is used as an antimicrobial agent.
 10. The method ofclaim 1, wherein the irradiated at least one oxidizing agent is used asa bleaching agent.
 11. (canceled)
 12. The method of claim 1, wherein theradiation is applied to the at least one oxidizing agent before the atleast one oxidizing agent is applied to the target liquid, the targetliquid furthers a photo oxidization reaction that generates one or moreof hydrogen and its isotopes, and oxygen and its isotopes andelectronically modifies oxygen derivatives, ROS, trioxygen, and freeradicals or produces additional reactions, and the further or additionalreactions are not dependent on continued or additional exposure ofradiation.
 13. The method of claim 1, wherein the radiation is appliedto the at least one oxidizing agent after the at least one oxidizingagent is applied to the target liquid so that the trioxygen and the oneor more of hydrogen and its isotopes, and oxygen and its isotopes aregenerated after the at least one oxidizing agent is applied to thetarget liquid, and a photo oxidation reaction is not initiated.
 14. Themethod of claim 13, wherein the generating of the one or more ofhydrogen and its isotopes, and oxygen and its isotopes andelectronically modifying oxygen derivatives, ROS, trioxygen, and freeradicals produces a desired effect at a predetermined time afterapplication of the at least one oxidizing agent to the target liquid,and the predetermined time is variable.
 15. The method of claim 1,wherein the generating of one or more of hydrogen and its isotopes, andoxygen and its isotopes and electronically modifying oxygen derivatives,ROS, trioxygen, and free radicals occurs in a sealed container wherebygases created by the generating of the one or more of RNS, hydrogen andits isotopes, and oxygen and its isotopes and electronically modifyingoxygen derivatives, ROS, trioxygen, and free radicals are not allowed toescape.
 16. The method of claim 1, wherein the at least one oxidizingagent is selected from Oxygen (O₂), trioxygen (O₃), Hydrogen (H),Hydrogen peroxide (H₂O₂) or other inorganic peroxides, Fenton's reagent,Fluorine (F₂), chlorine (Cl₂), or other halogens, Nitric acid (HNO₃) ornitrate compounds, Sulfuric acid (H₂SO₄), Peroxydisulfuric acid(H₂S₂O₈), Peroxymonosulfuric acid (H₂SO₅), or other Sulfur compounds,Hypochlorite, Chlorite, chlorate, perchlorate, or other analogoushalogen compounds, chromic or dichromic acids, chromium trioxide,pyridinium chlorochromate (PCC), chromate, or dichromate compounds, orother hexavalent chromium compounds, potassium permanganate (KMnO₄),Sodium perborate, or other Permanganate compounds, Nitrous oxide (N₂O),Nitrogen dioxide/Dinitrogen tetroxide (NO₂/N₂O₄), urea, Potassiumnitrate (KNO₃), Sodium bismuthate (NaBiO₃), ceric ammonium nitrate,ceric sulfate, or other Cerium (IV) compounds, peracetic acid, and Leaddioxide (PbO₂).
 17. The method of claim 1, further comprising selectingthe at least one oxidizing agent dependent on properties of whether thetarget liquid to be treated is under aerobic or anaerobic conditions,the pH of the target liquid, temperature of the target liquid, salinityof the target liquid, consortium or population characteristics oforganisms or micro-organism present, content of the target liquid,content of any biofilms associated with the target liquid or otherwise acomposition on the target liquid.
 18. The method of claim 1, wherein theat least one oxidizing agent further comprises at least one othersubstance for a desired process includes antimicrobial properties,anticorrosion properties, anti-neoplastic properties, thermalproperties, explosive properties, precipitation properties,electrochemical properties, power generation properties or other desiredeffects obtained in combination with the desired process.
 19. (canceled)20. A system configured to perform the steps of the method of claim 1,comprising: a reaction area, in which the at least one oxidizing agentfunctions together with the radiation of certain wavelengths to lead toa synergistic reaction, so that the products of the reaction can becollected and separated any time during the reaction if desired, atleast one oxidizing agent introducing component for applying the atleast one oxidizing agent to the target, and at least one radiationemitting component for creating the radiation wherein wavelengths thatcan photodissociate, eliminate, or reduce trioxygen are excluded fromthe radiation.
 21. The system of claim 20, further comprising: at leastone or more sensors or other devices to indicate, detect, or inform ofone or more of the following properties of the target or storage orenvironment: pH, temperature, salinity, density, trioxygenconcentration, oxygen concentration, hydrogen concentration, oxidizingagent concentration, flow rate, microbial content, presence or absent ofbacterial species, presence or absent of corrosive metabolites orotherwise corrosive substance, identification of a gas, presence orabsent of an aqueous environment, presence or absent of high, low, orotherwise concentration of bacterial or non-bacterial, biomass ornon-biomass, microbial content, or location of biofilms.
 22. The systemof claim 20, wherein the at least one radiation emitting componentemits, delivers, produces, or otherwise facilitates the radiationbetween 100 nanometers and 1200 nanometers, independently, simultaneous,continuously, or intermittently.
 23. The system of claim 20, wherein theat least one radiation emitting component is suspended, adjacent to,inside of, surrounding or associated with a container, structure or areaof the at least one oxidizing agent, or the target or supported in atarget container, so that the at least one radiation emitting componentis physically close to the at least one oxidizing agent and/or thetarget.
 24. The system of claim 20, wherein the at least one radiationemitting component adjusts the radiation wavelengths, intensity,duration or location relative to the target on the basis of any one ormore of the density and light absorbing or reflection quality of thetarget to be treated, the size, shape, or composition of the reactionarea, conditions or properties of the environment, whether the target isunder aerobic or anaerobic conditions, pH, temperature, salinity of thetarget, consortium or population characteristics of any organisms ormicro-organisms present in the target, the microbial content of thetarget, and the microbial content of any biofilm present in the target,the reaction area, or the environment.
 25. The system of claim 20,wherein concentration, temperature, viscosity, PH and/or other variablesof the at least one oxidizing agent are adjusted to produce the desiredreaction or results.
 26. The system of claim 20, wherein the at leastone oxidizing agent and the target is a liquid, solid, gas, plasma orcombination thereof, either independently or simultaneously.
 27. Thesystem of claim 20, wherein the reaction is affected or initiated by theaddition of other catalysts.
 28. The system of claim 20, wherein theradiation is directly or indirectly applied to the at least oneoxidizing agent, the target, or the combination thereof, and theindirect application is application by fiber optics cable, reflection,or other means of transmission.
 29. The system of claim 20, wherein theduration of the radiation includes less than 1 second, greater than 1second, continuous, pulsed, or intermittent.
 30. The system of claim 1,wherein the at least one oxidizing agent is heated or cooled to activateand/or inactivate enzymes present in the target.
 31. The methodaccording to claim 1, wherein the method is performed without applyingenzymes, stabilizers or other substance that affect the overall reactionrate.
 32. The method according to claim 1, wherein the method isperformed by applying radiation having a wavelength in a range ofgreater than 307 nm to less than 599 nm with wavelengths of 402 nm and452 nm being excluded.
 33. The method according to claim 16, wherein theat least one oxidizing agent is hydrogen peroxide.